Cosmetic raw material cosmetic product and method for manufacturing a cosmetic product

ABSTRACT

A cosmetic raw material using a vinyl polymer containing carbosiloxane dendritic structures and fluorinated organic group as the main or most important ingredient, a cosmetic product obtained by compounding with the cosmetic raw material, and a method for manufacturing a cosmetic product, in which said cosmetic raw material is mixed with other cosmetic raw materials. The cosmetic raw material exhibits superior compounding stability in cosmetic products and capable of imparting excellent feel and surface protective properties to cosmetic products. The cosmetic product exhibits superior adhesion to the hair and skin.

The present invention relates to a cosmetic raw material, a cosmeticproduct, and a method for manufacturing a cosmetic product.Specifically, it relates to a cosmetic raw material exhibiting superiorcompounding stability in cosmetic products and capable of impartingexcellent feel on application and surface protective properties tocosmetic products, to a cosmetic product obtained by compounding withthe cosmetic raw material, and to a method for manufacturing thecosmetic product. Cosmetic where used herein includes the application tothe body for purposes other than beautifying, such as administering ofmaterials to skin.

In the past, vinyl co-polymers of radical polymerizable monomers andorganopolysiloxanes containing radical polymerizable groups have beenknown to be used as cosmetic raw materials. For instance, JapanesePatent Application Publication No. Hei 5-000924 offers a base oil for ahair dressing agent consisting of a vinyl polymer obtained bypolymerizing methacrylic acid and tertiary butyl acrylate with adimethylpolysiloxane oligomer containing methacrylic groups. While thisvinyl co-polymer does give water repellent properties and slip tocosmetic products, its compatibility with other cosmetic raw materialsis low, and its compounding stability is inferior. In addition, as aresult of insufficient adhesion to the hair and skin, it easily washesoff and has inferior surface protective properties. A cosmetic rawmaterial using a vinyl polymer with carbosiloxane dendritic structuresin side chains as its main ingredient has been proposed with a view tosolve such problems (see EP 963751). However, the water repellency, oilrepellency, skin-oil resistance, and adhesion to the hair and skin ofsuch a vinyl polymer are still not completely satisfactory.

The inventors arrived at the present invention as a result of in-depthinvestigations aimed at overcoming the above-described problems. Namely,it is an object of the present invention to provide a cosmetic rawmaterial exhibiting superior compounding stability in cosmetic productsand capable of imparting excellent feel on application and surfaceprotective properties to cosmetic products, a cosmetic productexhibiting superior adhesion to the hair and skin obtained bycompounding with said cosmetic raw material, and a method formanufacturing the cosmetic product.

The present invention relates to a cosmetic raw material using a vinylpolymer containing carbosiloxane dendritic structures and fluorinatedorganic groups as its main or most important ingredient, a cosmeticproduct obtained by compounding with the cosmetic raw material,preferably by combining it with other raw materials or other cosmeticingredients and a method for manufacturing the cosmetic product, inwhich the cosmetic raw material is mixed with other cosmetic ingredientsor other raw materials.

First of all, explanations are provided regarding the cosmetic rawmaterial of the present invention. The vinyl polymer used in thecosmetic raw material of the present invention is characterized bycontaining carbosiloxane dendritic structures and fluorinated organicgroups. Structures, in which vinylic polymerized units constitute thebackbone and carbosiloxane dendritic structures along with fluorinatedorganic groups are attached in side chains, are particularly preferable.In this invention, the carbosiloxane dendritic structures are highmolecular structures obtained by regular high-degree branching from asingle silicon atom. Structures represented by the formula(I):

are suggested as a specific example (see EP1055674). In the formula(I),Z is a divalent organic group exemplified by alkylene, arylene,aralkylene, ester-containing divalent organic groups, ether-containingdivalent organic groups, ketone-containing divalent organic groups, andamide-containing divalent organic groups. Among the above, organicgroups represented by the following formulas are preferable.

where R⁹ is an alkylene group with 1 to 10 carbon atoms exemplified bymethylene, ethylene, propylene, and butylene. Among the above, methyleneand propylene are preferable. R¹⁰ is an alkyl group with 1 to 10 carbonatoms exemplified by methyl, ethyl, propyl, and butyl. Among the above,methyl is preferable. R¹¹ is an alkylene group with 1 to 10 carbon atomsexemplified by methylene, ethylene, propylene, and butylene. Among theabove, ethylene is preferable. The subscript <<d>> is an integer of 0 to4, and <<e>> is 0 or 1. In the formula(I), the subscript <<p>> is 0or 1. R¹ is an aryl or alkyl group with 1 to 10 carbon atoms, with alkylgroups exemplified by methyl, ethyl, propyl, butyl, pentyl, isopropyl,isobutyl, cyclopentyl, and cyclohexyl groups, and aryl groupsexemplified by phenyl and naphthyl groups. Among the above, methyl andphenyl are preferable, and methyl is particularly preferable. X^(i) is asilylalkyl group represented by the following formula(II):

In the formula(II), R¹ is the same as above. R² is an alkylene groupwith 2 to 10 carbon atoms exemplified by ethylene, propylene, butylene,hexylene, and other linear alkylene groups; methylmethylene,methylethylene, 1-methylpentylene, 1,4-dimethylbutylene, and otherbranched alkylene groups. Among the above, ethylene, methylethylene,hexylene, 1-methylpentylene, and 1,4-dimethylbutylene are preferable. R³is an alkyl group with 1 to 10 carbon atoms exemplified by methyl,ethyl, propyl, butyl, and isopropyl. X^(i+1) is a group selected fromthe group comprising hydrogen atoms, aryl groups and alkyl groups with 1to 10 carbon atoms, and the above-mentioned silylalkyl groups X^(i),with the alkyl and aryl groups exemplified by the same groups as theabove-described R¹. The superscript <<i>> is an integer of 1 to 10indicating the generation of the silylalkyl group, starting in eachcarbosiloxane dendritic structure with a value of 1 for the X^(i) groupin the formula(I), and <<a^(i)>> is an integer of 0 to 3.

On the other hand, groups obtained by substituting fluorine atoms forsome or all of the hydrogen atoms of methyl, ethyl, propyl, isopropyl,butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, cyclohexyl,heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl,hexadecyl, octadecyl, and other alkyl groups with 1 to 20 carbon atoms,as well as alkyloxyalkylene groups with 6 to 22 carbon atoms, aresuggested as the fluorinated organic groups.

Groups represented by the formula: —(CH₂)_(x)—(CF₂)_(y)—R¹³ aresuggested as examples of fluoroalkyl groups obtained by substitutingfluorine atoms for the hydrogen atoms of alkyl groups. In the formula,the subscript <<x>> is 0, 1, 2, or 3 and <<y>> is an integer of 1 to 20.R¹³ is an atom or group selected from a hydrogen atom, a fluorine atom,—CH(CF₃)₂— or —CF(CF₃)₂. Such fluorine-substituted alkyl groups areexemplified by linear or branched polyfluoroalkyl or perfluoroalkylgroups represented by the formulas shown below.

-   —CF₃, —C₂F₅, -nC₃F₇, —CF(CF₃)₂, -nC₄F₉, —CF₂CF(CF₃)₂, -nC₅F₁₁,    -nC₆F₁₃, -nC₈F₁₇,-   —CH₂CF₃, —CH(CF₃)₂, —CH₂CH(CF₃)₂, —CH₂(CF₂)₂F, —CH₂(CF₂)₃F,    —CH₂(CF₂)₄F,-   —CH₂(CF₂)₆F, —CH₂(CF₂)₈F, —CH₂CH₂CF₃, —CH₂CH₂(CF₂)₂F,    —CH₂CH₂(CF₂)₃F,-   —CH₂CH₂(CF₂)₄F, —CH₂CH₂(CF₂)₆F, —CH₂CH₂(CF₂)₈F, —CH₂CH₂(CF₂)₁₀F,-   —CH₂CH₂(CF₂)₁₂F, —CH₂CH₂(CF₂)₁₄F, —CH₂CH₂(CF₂)₁₆F, —CH₂CH₂CH₂CF₃,-   —CH₂CH₂CH₂(CF₂)₂F, —CH₂CH₂CH₂(CF₂)₂H, —CH₂(CF₂)₄H, and    —CH₂CH₂(CF₂)₃H.

Groups represented by the general formula—CH₂CH₂—(CF₂)_(m)—CFR¹⁴—[OCF₂CF(CF₃)]_(n)—OC₃F₇ are suggested asfluoroalkyloxyfluoroalkylene groups obtained by substituting fluorineatoms for the hydrogen atoms of alkyloxyalkylene groups. In the formula,the subscript <<m>> is 0 or 1, <<n>> is 0, 1, 2, 3, 4, or 5, and R¹⁴ isa fluorine atom or CF₃. Such fluoroalkyloxyfluoroalkylene groups areexemplified by perfluoroalkyloxyfluoroalkylene groups represented by theformulas shown below. —CH₂CH₂CF(CF₃)—[OCF₂CF(CF₃)]_(n)—OC₃F₇,—CH₂CH₂CF₂CF₂— [OCF₂CF(CF₃)]_(n)—OC₃F₇.

Fluoroalkyl groups in general, and fluoroalkyl groups with 1 to 14carbon atoms in particular, are preferable among such fluorinatedorganic groups from the standpoint of improving the oil repellency andskin-oil resistance of the cosmetic raw material of the presentinvention. In addition, fluoroalkyl groups with 1 to 5 carbon atoms,and, more specifically, groups such as —CH₂CF₃, are preferable when itis desirable to reduce stickiness.

To make compounding easier, the number average molecular weight of thevinyl polymer used in the present invention should preferably be between3,000 and 2,000,000, and, even more preferably, between 5,000 and800,000. In addition, the polymer can be used in various forms, forexample, in liquid, rubber, paste, solid, or powder form. Whencompounding in a cosmetic product, it is preferable to use it in powderform or in the form of a suspension or solution prepared by dissolvingin a solvent.

This type of vinyl polymer is obtained by adding, if desired ornecessary, (B) a vinyl monomer that does not have fluorinated organicgroups in the molecule to (A) a vinyl monomer containing fluorinatedorganic groups in the molecule and (C) a carbosiloxane dendrimercontaining radical polymerizable organic groups represented by thegeneral formula(III):

wherein Y is a radical polymerizable organic group and R¹ and X^(i) arethe same as above and subjecting them to co-polymerization.

The vinyl monomers (A) containing fluorinated organic groups in themolecule are preferably monomers represented by the general formula:CH₂═CR¹⁵COOR^(f). In the formula, R¹⁵ is a hydrogen atom or methylgroup, R^(f) is a fluorinated organic group exemplified by theabove-described fluoroalkyl and fluoroalkyloxyfluoroalkylene groups.Compounds represented by the formulas shown below are suggested asspecific examples of Component (A). In the formulas shown below, <<z>>is an integer of 1 to 4.

-   CH₂═CCH₃COO—CF₃. CH₂═CCH₃COO—C₂F₅. CH₂═CCH₃COO— nC₃F₇-   CH₂═CCH₃COO—CF(CF₃)₂. CH₂═CCH₃COO— nC₄F₉-   CH₂═CCH₃COO—CF₂ CF(CF₃)₂. CH₂═CCH₃COO— nC₅F₁₁.-   CH₂═CCH₃COO-nC₆F₁₃. CH₂═CCH₃COO— nC₈FI₇ CH₂═CCH₃COO—CH₂CF₃.-   CH₂═CCH₃COO—CH(CF₃)₂. CH₂═CCH₃COO—CH₂CH(CF₃)₂.-   CH₂═CCH₃COO—CH₂ (CF₂)₂F.-   CH₂═CCH₃COO—CH₂(CF₂)₃F. CH₂═CCH₃COO—CH₂ (CF₂)₄F.-   CH₂═CCH₃COO—CH₂(CF₂)₆F. CH₂═CCH₃COO—CH₂ (CF₂)₈F.-   CH₂═CCH₃COO—CH₂CH₂CF₃. CH₂═CCH₃COO—CH₂CH₂ (CF₂)₂F.-   CH₂═CCH₃COO—CH₂CH₂ (CF₂)₃F. CH₂═CCH₃COO—CH₂CH₂ (CF₂)₄F.-   CH₂═CCH₃COO—CH₂CH₂ (CF₂)₆F. CH₂═CCH₃COO—CH₂CH₂ (CF₂)_(g)F.-   CH₂═CCH₃COO—CH₂CH₂(CF₂)₁₀F. CH₂═CCH₃COO—CH₂CH₂ (CF₂)₁₂F.-   CH₂═CCH₃COO—CH₂CH₂ (CF₂)₁₄F. CH₂═CCH₃COO—CH₂CH₂ (CF₂)₁₆F.-   CH₂═CCH₃COO—CH₂CH₂CH₂CF₃. CH₂═CCH₃COO—CH₂CH₂CH₂ (CF₂)₂F.-   CH₂═CCH₃COO—CH₂CH₂CH₂ (CF₂)₂H. CH₂═CCH₃COO—CH₂ (CF₂)₄H.-   CH₂═CCH₃COO—CH₂CH₂(CF₂)₃H.-   CH₂═CCH₃COO—CH₂CH₂CF(CF₃)—[OCF₂ CF(CF₃)]z-OC₃F₇.-   CH₂═CCH₃COO—CH₂CH₂CF₂CF₂—[OCF₂CF(CF₃)]z-OC₃F₇.-   CH₂═CHCOO—CF₃. CH₂═CHCOO—C₂ F₅. CH₂═CHCOO-nC₃F₇. CH₂═CHCOO—CF(CF₃)₂.-   CH₂═CHCOO-nC₄F₉. CH₂═CHCOO—CF₂CF(CF₃)₂. CH₂═CHCOO-nC₅F₁₁.-   CH₂═CHCOO-nC₆F₃ CH₂═CHCOO-nC₈F₁₇. CH₂═CHCOO—CH₂CF₃.-   CH₂═CHCOO—CH(CF₃)₂ CH₂═CHCOO—CH₂CH(CF₃)₂. CH₂═CHCOO—CH₂(CF₂)₂F.-   CH₂═CHCOO—CH₂(CF₂)₃F. CH₂═CHCOO—CH₂(CF₂)₄F. CH₂═CHCOO—CH₂(CF₂)₆F.-   CH₂═CHCOO—CH₂ (CF₂)₈ F. CH₂═CHCOO—CH₂CH₂CF₃.-   CH₂═CHCOO—CH₂CH₂ (CF₂)₂F.-   CH₂═CHCOO—CH₂CH₂ (CF₂)₃F. CH₂═CHCOO—CH₂CH₂ (CF₂)₄F.-   CH₂═CHCOO—CH₂CH₂ (CF₂)₆F. CH₂═CHCOO—CH₂CH₂ (CF₂)₈F.-   CH₂═CHCOO—CH₂CH₂(CF₂)₁₀F. CH₂═CHCOO—CH₂CH₂(CF₂)₁₂F.-   CH₂═CHCOO—CH₂CH₂ (CF₂)₁₄F. CH₂═CHCOO—CH₂CH₂ (CF₂)₁₆F.-   CH₂═CHCOO—CH₂CH₂CH₂CF₃. CH₂═CHCOO—CH₂CH₂ CH₂ (CF₂)₂F.-   CH₂═CHCOO—CH₂CH₂CH₂ (CF)₂H. CH₂═CHCOO—CH₂(CF₂)₄H.-   CH₂═CHCOO—CH₂CH₂(CF₂)₃H.-   CH₂═CHCOO—CH₂CH₂CF(CF₃)—[OCF₂ CF(CF₃)]z-OC₃ F₇.-   CH₂═CHCOO—CH₂CH₂CF₂CF₂—[OCF₂ CF(CF₃)]z-OC₃ F₇.

Among the above, vinyl polymers represented by the formulas shown beloware preferable.

-   CH₂═CHCOO—CH₂CH₂ (CF₂)₆F CH₂═CHCOO—CH₂CH₂ (CF₂)₈F.-   CH₂═CCH₃COO—CH₂CH₂ (CF₂)₆ F. CH₂═CCH₃COO—CH₂CH₂ (CF₂)₈ F.-   CH₂═CHCOO—CH₂CF₃. CH₂═CCH₃COO—CH₂CF₃

Vinyl polymers represented by the formulas shown below are particularlypreferable.

-   CH₂═CHCOO—CH₂CF₃. CH₂═CCH₃COO—CH₂CF₃.

The vinyl monomers (B) that do not contain fluorinated organic groups inthe molecule may be any monomers having radical polymerizable vinylgroups, which are exemplified, for instance, by methyl acrylate, methylmethacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate,n-propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, andother lower alkyl acrylates or methacrylates; glycidyl acrylate,glycidyl methacrylate; n-butyl acrylate, n-butyl methacrylate, isobutylacrylate, isobutyl methacrylate, tert-butyl acrylate, tert-butylmethacrylate, n-hexyl acrylate, n-hexyl methacrylate, n-hexyl acrylate,n-hexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate,2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octylmethacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate,stearyl methacrylate, and other higher acrylates and methacrylates;vinyl acetate, vinyl propionate, and other lower fatty acid vinylesters; vinyl butyrate, vinyl caproate, vinyl 2-ethylhexanoate, vinyllaurate, vinyl stearate, and other higher fatty acid esters; styrene,vinyltoluene, benzyl acrylate, benzyl methacrylate, phenoxyethylacrylate, phenoxyethyl methacrylate, vinyl pyrrolidone, and otheraromatic vinyl monomers; dimethyl aminoethyl acrylate, dimethylaminoethyl methacrylate, diethyl aminoethyl acrylate, diethyl aminoethylmethacrylate, and other amino-containing vinyl monomers; acrylamide,methacrylamide, N-methylol acrylamide, N-methylol methacrylamide,N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide,isobutoxymethoxyacrylamide, isobutoxymethoxymethacrylamide, N,N-dimethylacrylamide, N,N-dimethyl methacrylamide, and other amide-containingvinyl monomers; hydroxyethyl acrylate, hydroxyethyl methacrylate,acrylic acid hydroxypropyl alcohol, methacrylic acid hydroxypropylalcohol, and other hydroxyl-containing vinyl monomers; acrylic acid,methacrylic acid, itaconic acid, crotonic acid, fumaric acid, maleicacid, and other carboxylic acid-containing vinyl monomers;tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate,butoxyethyl acrylate, butoxyethyl methacrylate, ethoxydiethylene glycolacrylate, ethoxydiethylene glycol methacrylate, polyethylene glycolacrylate, polyethylene glycol methacrylate, polypropylene glycolmonoacrylate, polypropylene glycol monomethacrylate, hydroxybutyl vinylether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, and other etherbond-containing vinyl monomers; acryloxypropyltrimethoxysilane,methacryloxypropyltrimethoxysilane, polydimethylsiloxanes containingacryl or methacryl groups at the one of the terminal ends,polydimethylsiloxanes containing alkenylaryl groups at the one of theterminal ends, and other unsaturated group-containing siliconecompounds; butadiene; vinyl chloride; vinylidene chloride;acrylonitrile, methacrylonitrile; dibutyl fumarate; maleic anhydride;dodecyl succinic anhydride; acryl glycidyl ether, methacryl glycidylether, 3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethylmethacrylate; alkali metal salts, ammonium salts, and organic aminesalts of acrylic acid, methacrylic acid, itaconic acid, crotonic acid,fumaric acid, maleic acid, and other radical polymerizable unsaturatedcarboxylic acids, radical polymerizable unsaturated monomers containingsulfonic acid groups such as styrenesulfonic acid as well as theiralkali metal salts, ammonium salts, and organic amine salts; quaternaryammonium salts derived from acrylic acid or methacrylic acid such as2-hydroxy-3-methacryloxypropyl trimethylammonium chloride, methacrylicacid esters of a tertiary amine-containing alcohol such as methacrylicacid diethylamine ester and their quaternary ammonium salts.

In addition, it is also possible to use as vinyl monomers (B)polyfunctional vinyl monomers, which are exemplified, for instance, bytrimethylolpropane triacrylate, trimethylolpropane trimethacrylate,pentaerythritol triacrylate, pentaerythritol trimethacrylate, ethyleneglycol diacrylate, ethylene glycol dimethacrylate, tetraethylene glycoldiacrylate, tetraethylene glycol dimethacrylate, polyethylene glycoldiacrylate, polyethylene glycol dimethacrylate, 1,4-butanedioldiacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol diacrylate,1,6-hexanediol dimethacrylate, neopentyl glycol diacrylate, neopentylglycol dimethacrylate, trimethylolpropane trioxyethyl acrylate,trimethylolpropane trioxyethyl methacrylate,tris(2-hydroxyethyl)isocyanurate diacrylate,tris(2-hydroxyethyl)isocyanurate dimethacrylate,tris(2-hydroxyethyl)isocyanurate triacrylate,tris(2-hydroxyethyl)isocyanurate trimethacrylate, polydimethylsiloxanehaving both ends of the molecular chain blocked by alkenylaryl groups,and other unsaturated group-containing silicone compounds.

As concerns the above-mentioned ratio, in which component (A) andcomponent (B) are co-polymerized, the weight ratio of component (A) tocomponent (B) should be within the range of from 0.1:99.9 to 100:0, and,preferably, within the range of from 1:99 to 100:0.

The carbosiloxane dendrimer (C) is represented by the generalformula(III), indicated above. In that formula(III), Y is a radicalpolymerizable organic group, the type of which is not subject to anyspecial limitations so long as this is an organic group capable ofundergoing a radical addition reaction. Acryl and methacryl-containingorganic groups, alkenylaryl-containing organic groups, or alkenyl groupswith 2 to 10 carbon atoms represented by the general formulas shownbelow are suggested as specific examples.

In the formulas, R⁴ and R⁶ are hydrogen atoms or methyl groups, R⁵ andR⁸ are alkylene groups with 1 to 10 carbon atoms, and R⁷ is an alkylgroup with 1 to 10 carbon atoms. The subscript <<b>> is an integer of 0to 4, and <<c>> is 0 or 1. Acryloxymethyl, 3-acryloxypropyl,methacryloxymethyl, 3-methacryloxypropyl, 4-vinylphenyl, 3-vinylphenyl,4-(2-propenyl)phenyl, 3-(2-propenyl)phenyl, 2-(4-vinylphenyl)ethyl,2-(3-vinylphenyl)ethyl, vinyl, allyl, methallyl, and 5-hexenyl aresuggested as examples of such radical polymerizable organic groups. Thesuperscript <<i>> in the formula(II), which is an integer of 1 to 10, isthe generation number of said silylalkyl group, in other words, thenumber of times the silylalkyl group is repeated. Thus, thecarbosiloxane dendrimer of this component with a generation number of 1is represented by the general formula:

(wherein Y, R¹, R², and R³ are the same as above, and R¹² is a hydrogenatom or the same as R¹ described above. The subscript <<a¹>> is aninteger of 0 to 3, the average total of <<a¹>> per molecule being 0 to7). Carbosiloxane dendrimers of this component with a generation numberof 2 are represented by the general formula:

(wherein Y, R¹, R², R³, and R¹² are the same as above, and thesubscripts <<a¹>> and <<a²>> are integers of 0 to 3, the average totalof <<a¹>> and <<a²>> per molecule being 0 to 25).

Carbosiloxane dendrimers of this component with a generation number of 3are represented by the general formula:

(wherein Y, R¹, R², R³, and R¹² are the same as above and the subscripts<<a¹>>, <<a²>> and <<a³>> are integers of 0 to 3, the average total of<<a¹>>, <<a²>), and <<a³>> per molecule being 0 to 79).

Component (C) is exemplified by carbosiloxane dendrimers represented bythe average composition formulas shown below.

The carbosiloxane dendrimers of component (C) can be prepared using thepreparation method for branched siloxane/silalkylene copolymersdescribed in EP1055674. For example, they can be prepared by subjectingalkenyl-containing organic silicon compounds and silicon compoundscontaining silicon-bonded hydrogen atoms represented by the generalformula:

(where R¹ and Y are the same as above) to a hydrosilation reaction. Forinstance, 3-methacryloxypropyl tris(dimethylsiloxy)silane,3-acryloxypropyl tris(dimethylsiloxy)silane, and 4-vinylphenyltris(dimethylsiloxy)silane are used as the silicon compounds representedby the formula above. Vinyltris(trimethylsiloxy)silane,vinyltris(dimethylphenylsiloxy)silane, and5-hexenyltris(trimethylsiloxy)silane are used as the alkenyl-containingorganic silicon compounds. In addition, it is preferable to conduct thehydrosilation reaction in the presence of a transition metal catalyst,such as chloroplatinic acid and platinum/vinylsiloxane complex.

The co-polymerization ratio of component (C), in terms of its weightratio with respect to the total of component (A) and component (B),should be in the range of from 0.1:99.9 to 99.9:0.1, preferably, in therange of from 1:99 to 99:1, and, even more preferably, in the range offrom 5:95 to 95:5.

The vinyl polymers used in the present invention are prepared byco-polymerizing the above-described component (A), component (B), andcomponent (C) or by polymerizing component (A) and component (C).Radical polymerization and ion polymerization can be used as thepolymerization methods, with radical polymerization being preferable andsolution polymerization being especially suitable. Solutionpolymerization is carried out by reacting the above-described componentsin a solvent in the presence of a radical initiator for 3 to 20 hours ata temperature of 50 to 150° C. Solvents used at such time areexemplified by hexane, octane, decane, cyclohexane, and other aliphatichydrocarbons; benzene, toluene, xylene, and other aromatic hydrocarbons;diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, and otherethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutylketone, and other ketones; methyl acetate, ethyl acetate, butyl acetate,isobutyl acetate, and other esters; methanol, ethanol, isopropylalcohol, butanol, and other alcohols; octamethylcyclotetrasiloxane,decamethylcyclopentasiloxane, hexamethyldisiloxane,octamethyltrisiloxane, and other organosiloxane oligomers. The radicalinitiators are publicly known conventional compounds used for radicalpolymerization, specifically exemplified by2,2′-azobis(isobutyronitrile), 2,2′-azobis(2-methylbutyronitrile),2,2′-azobis(2,4-dimethylvaleronitrile), and other azobis compounds;benzoyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate,tert-butyl peroxy-2-ethylhexanoate, and other organic peroxides. Theradical initiators can be used singly or in combination as two or moreinitiators mixed together. The amount of the radical initiator ispreferably in the range of from 0.1 to 5 parts by weight per 100 partsby weight of the total of the above-described component (A) to component(C). In addition, chain transfer agents can be added duringpolymerization. Specific example of the chain transfer agents include2-mercaptoethanol, butylmercaptan, n-dodecylmercaptan,3-mercaptopropyltrimethoxysilane, mercaptopropyl-containingpolydimethylsiloxanes, and other mercapto compounds; methylene chloride,chloroform, carbon tetrachloride, butyl bromide,3-chloropropyltrimethoxysilane, and other halogen compounds. Inaddition, after polymerization, it is preferable to remove residualunreacted vinyl monomers by treating the polymer under reduced pressureand heating.

In addition, in order to further improve the adherence or adhesion ofthe vinyl polymer to the skin and hair, as well as impart it withsuitable properties for easy washability after application, amino groupscan be introduced in the side chains of the vinyl polymer by using, aspart of component (B), vinyl monomers containing amino groups, such asdimethyl aminoethyl acrylate, dimethyl aminoethyl methacrylate, diethylaminoethyl acrylate, and diethyl aminoethyl methacrylate, and thenperforming modification with potassium monochloroacetate, ammoniummonochloroacetate, aminomethylpropanol salt of monochloroacetic acid,triethanolamine salt of monobromoacetic acid, sodiummonochloropropionate, and other alkali metal salts of halogenated fattyacids; otherwise, carboxylic acid groups can be introduced in the sidechains of the vinyl polymer by using, as part of component (B), vinylmonomers containing carboxylic acids, such as acrylic acid, methacrylicacid, itaconic acid, crotonic acid, fumaric acid, and maleic acid, etc.,and then neutralizing the product with triethylamine, diethylamine,triethanolamine, and other amines.

The cosmetic raw material of the present invention uses theabove-described vinyl polymer containing carbosiloxane dendriticstructures and fluorinated organic groups as its main or most importantingredient. Solutions or dispersions obtained by adding liquids selectedfrom the group comprising silicone oil, organic oil, alcohol, and waterto the vinyl polymer are suggested as examples of such materials. Theviscosity of such a solution or dispersion at 25° C. is preferably inthe range of from 10 to 1,000,000,000 mPa·s, and, even more preferably,in particular, from the standpoint of improving the feel of the cosmeticproduct, in the range of from 100 to 500,000,000 mPa·s. In addition, theconcentration of the vinyl polymer in the dispersion or solution istypically in the range of from 0.1 wt % to 95 wt %, and, preferably, inthe range of from 1 wt % to 85 wt %. Furthermore, to make compoundingand handling easier, it should preferably be in the range of from 5 wt %to 75 wt %.

Examples of the silicone oils include, for instance,dimethylpolysiloxane having both ends of the molecular chain blocked bytrimethylsiloxy groups, dimethylsiloxane/methylphenylsiloxane copolymerhaving both ends of the molecular chain blocked by trimethylsiloxygroups, dimethylsiloxane/methyl(3,3,3-trifluoropropyl)siloxane copolymerhaving both ends of the molecular chain blocked by trimethylsiloxygroups, and other linear non-reactive silicone oils, as well as cycliccompounds such as hexamethylcyclotrisiloxane,octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, anddodecamethylcyclohexasiloxane. In addition to the above-mentionednon-reactive silicone oils, one may use modified polysiloxanes havingpolyether, amino, silanol, and other functional groups in the sidechains or at the terminal ends of the molecular chain.

Examples of the organic oils include, for instance, liquid paraffin,isoparaffin, hexyl laurate, isopropyl myristate, myristyl myristate,cetyl myristate, 2-octyldodecyl myristate, isopropyl palmitate,2-ethylhexyl palmitate, butyl stearate, decyl oleate, 2-octyldodecyloleate, myristyl lactate, cetyl lactate, lanolin acetate, stearylalcohol, oleyl alcohol, avocado oil, almond oil, olive oil, cacaobutter, jojoba oil, sesame oil, soybean oil, Camellia oil, squalane,persic oil, castor oil, mink oil, cottonseed oil, coconut oil, egg yolkoil, beef tallow, pork fat, polypropylene glycol monooleate, neopentylglycol-2-ethylhexanoate, and other glycol ether oils; isostearic acidtriglyceride, coconut oil fatty acid triglyceride, and other polyhydricalcohol ester oils; polyoxyethylene lauryl ether, polyoxypropylene cetylether, and other polyoxyalkylene ether oils.

Although any alcohols used in cosmetic raw materials may be utilized,methanol, ethanol, butanol, isopropyl alcohol, and other lower alcoholsare preferable.

The vinyl polymer solution or suspension used in the cosmetic rawmaterial of the present invention can be easily prepared by mixingsilicone oil, organic oil, alcohol, or water with the vinyl polymer. Inaddition, these liquids may be present during the polymerization of thevinyl polymer. In this case, it may be necessary to completely eliminatetheir odor by removing all residual unreacted vinyl monomers bysubjecting the solution or dispersion to heat treatment under normal orreduced pressure. Moreover, pigments such as iron oxide and particles ofinorganic oxides, such as titanium oxide, silicon oxide, mica, talc,etc., which are allowed to be used as cosmetic ingredients in cosmeticmaterials, can be compounded or combined with the solutions anddispersions. In addition, in case of dispersions, surfactants may beadded in order to improve the dispersibility of the vinyl polymer. Suchsurfactants are exemplified by hexylbenzenesulfonic acid,octylbenzenesulfonic acid, decylbenzenesulfonic acid,dodecylbenzensulfonic acid, cetylbenzenesulfonic acid,myristylbenzenesulfonic acid, and their sodium salts and other anionicsurfactants; octyltrimethylammonium hydroxide, dodecyltrimethylammoniumhydroxide, hexadecyltrimethylammonium hydroxide,octyldimethylbenzylammonium hydroxide, decyldimethylbenzylammoniumhydroxide, dioctadecyldimethylammonium hydroxide, tallowtrimethylammonium hydroxide, coconut oil trimethylammonium hydroxide,and other cationic surfactants; nonionic surfactants based onpolyoxyalkylene alkyl ethers, polyoxyalkylene alkyl phenols,polyoxyalkylene alkyl esters, polyoxyalkylene sorbitan esters,polyesters and ethylene oxide adducts of polyethylene glycol,polypropylene glycol, and diethylene glycol trimethylnonanol; as well asmixtures of two or more of the above surfactants. In such dispersions,the average particle size of the vinyl polymer is preferably in therange of from 0.001 to 100 μm, and, even more preferably, in the rangeof from 0.01 to 50 μm. This is due to the fact that if the averageparticle size falls outside the indicated ranges, the feel produced onapplication by cosmetic products compounded with the polymer, and, inparticular, finger and skin feel, as well as its spreadability, tend tobe insufficient.

The cosmetic raw material of the present invention as described above ischaracterized by exhibiting superior stability in cosmetic products,imparting excellent feel on application and surface protectiveproperties to cosmetic products, and, furthermore, improving their waterrepellency and oil repellency. In particular, when used in skincosmetics, it has the advantage of superior water repellency, gas andmoisture permeability, as well as the advantage of being unlikely tocause an unnatural, sticky skinfeel while imparting a clean and neatsensation, and, when used as a hair cosmetic material, has the advantageof imparting water repellency and hair-setting properties. In addition,because of its superior skin-oil resistance, it is characterized bysignificantly improving adhesion to the skin and hair. Thus, thecosmetic raw material of the present invention is suitable for use as araw material for skin cosmetics and hair cosmetics.

Next, explanations are provided regarding the cosmetic product of thepresent invention. In a preferred aspect of the invention, the cosmeticproduct of the present invention is prepared by adding theabove-mentioned cosmetic raw material and consists of the cosmetic rawmaterial of the present invention and other cosmetic ingredients or rawmaterials. There are no limitations concerning the type etc. of thecosmetic product of the present invention so long as it is normallycalled a cosmetic product or cosmetic material. Specifically, skincosmetic materials, for instance, are exemplified by soaps, bodyshampoos, facial cleansing creams, and other cleansing cosmeticproducts; skin lotion, creams, cosmetic milk, packs, and other basiccosmetic products; face powders, foundations, and other base makeupcosmetic products, lipstick, cheek rouge, eye shadow, eyeliner, mascara,and other cosmetic products for the care of the eyes and eyebrows; nailpolish, and other nail cosmetic products; depilating agents, shavinglotions, anti-perspirants and deodorants, sunburn preventives, and otherspecial cosmetic products; perfumes, eau de cologne, and other scentedcosmetic products. In addition, shampoos, hair rinses, hair treatments,permanent wave agents, hair dressing agents, hair-growing agents, hairtonics, hair dyes, etc. are suggested as hair cosmetic materials.Furthermore, toothpastes and bathing agents are suggested as othercosmetic products. The forms, in which the cosmetic product is used, areexemplified by water base liquid formulations, oil base liquidformulations, milk formulations, crime formulations, foam formulations,semi-solid formulations, solid formulations, and powders. In addition,the product can be atomized in spray form.

Other cosmetic raw materials forming part of the cosmetic product of thepresent invention are exemplified, for instance, by avocado oil, almondoil, olive oil, cacao butter, beef tallow, sesame oil, wheat germ oil,safflower oil, shea butter, turtle oil, camellia oil, persic oil, castoroil, rapeseed oil, macadamia nut oil, mink oil, egg yolk oil, Japanesewax, coconut oil, hydrogenated oil, and other oils and fats; orangeroughy oil, carnauba wax, candelilla wax, whale wax, jojoba oil, montanwax, beeswax, lanolin, and other waxes; liquid paraffin, Vaseline,paraffin, ceresin, microcrystalline wax, squalane, and otherhydrocarbons; lauric acid, myristic acid, palmitic acid, stearic acid,oleic acid, behenic acid, undecylenic acid, oxystearic acid, linoleicacid, lanolinic acid, synthetic fatty acids, and other higher fattyacids; ethyl alcohol, isopropyl alcohol, lauryl alcohol, cetyl alcohol,cetostearyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol,lanolin alcohol, hydrogenated lanolin alcohol, hexyl decanol, octyldodecanol, isostearyl alcohol, and other alcohols; cholesterol,dihydrocholesterol, phytosterols, and other sterols; ethyl linoleate,isopropyl myristate, lanolin fatty acid isopropyl ester, hexyl laurate,myristyl myristate, cetyl myristate, octyl dodecyl myristate, decyloleate, octyl dodecyl oleate, hexyl decyl dimethyloctanoate, glyceryltri(caprylate/carprate), propylene glycol dioleate, glyceryltriisostearate, glyceryl triisooctanoate, cetyl lactate, myristyllactate, diisostearyl maleate, and other fatty acid esters; glycerin,propylene glycol, 1,3-butylene glycol, polyethylene glycol, sodium d,1-pyrrolidonecarboxylate, sodium lactate, sorbitol, sodium hyaluronate,and other humectants; higher fatty acid soaps, sulfuric acid ester saltsderived from higher alcohols, N-acyl glutamic acid salts, phosphoricacid ester salts, and other anionic surfactants; cationic surfactants;betaine, amino acid, imidazoline, lecithin-based, and other amphotericsurfactants; polyhydric alcohol ester-based, ethylene oxidecondensation-type, and other nonionic surfactants, and othersurfactants; iron oxides and other colored pigments; zinc oxides,titanium oxides, zirconium oxides, and other white pigments; mica, talc,cericite, and other skin-colored pigments; dimethylpolysiloxane,methylphenylpolysiloxane, octamethyltetracyclosiloxane,decamethylcyclopentasiloxane, polyether-modified silicone oils,amino-modified silicone oils, trimethylsilicic acid, and othersilicone-based materials; purified water; carrageenan, alginic acid,alginic acid salts, gum arabic, traganth gum, pectin, agar-agar, casein,starch, xanthan gum, polyvinyl alcohol, polyvinyl pyrrolidine,poly(meth)acrylic acid and its salts, poly(meth)acrylic acid esters andtheir derivatives, polyethylene glycol, vinyl acetate resins, and otherhigh molecular compounds; and, furthermore, thickening agents, gellingagents, anti-ageing agents, anti-static agents, pigment-moisturizingagents, dispersing agents, anti-fading agents, anti-precipitationagents, anti-sagging agents, UV absorbers, antibacterial agents,anti-inflammation agents, antiperspirants, antiseptics, perfumes,anti-oxidants, pH adjusting agents, aerosol agents, and cosmetictreatment components.

In addition, cured silicone particles can be also combined with thecosmetic product of the present invention. Particles of resin-like curedsilicone and rubber-like cured silicone are suggested as theabove-mentioned cured silicone particles. Resin-like cured siliconeparticles give a clean feel to the hair and skin while rubber-like curedproduct particles give an elastic feel to the skin. Resin-like curedsilicone particles are prepared by subjecting hydrolyzable silanes ortheir partial hydrolyzates to hydrolysis and condensation. Rubber-likecured silicone particles are prepared by cross-linking cross-linkablesilicone rubber compositions and then grinding the product into powder,or by dispersing cross-linkable silicone rubber compositions in asolvent such as water, etc., cross-linking it, and removing the solvent.Water base suspensions of cured silicone rubber particles are preferablefrom the standpoint of the ease of compounding. As far as methods ofmanufacture are concerned, suggested techniques include dispersingrubber-like cured silicone particles in water using surface activeagents etc. or dispersing cross-linkable silicone rubber compositions inwater and then cross-linking them. In addition, the amount of the addedparticles should be sufficient to make their content in the cosmeticproduct fall the range of from 0.1 to 99 wt %, and, more preferably,from 0.2 to 85 wt %.

Because of the particularly good adherence to skin, the cosmetic rawmaterial is also very useful in applications where it may be applied toskin in the form of a topical application, for example a patch, whichmay be used to deposit or apply a component to the skin. Examples ofsuitable uses include the use as or in conjunction with a patch to applycosmetic, or even active ingredients to the skin or via the skin to thebody. Such patches are known and have been described in the art togetherwith ways of making and applying them, including for example EP 667382,in which ways of using materials as pressure sensitive adhesives for useas or in conjunction with patches have also been described. The cosmeticraw material could be used for similar purposes, either alone or inconjunction with other suitable ingredients, which have been describedin the art. The cosmetic products of the present invention can beprepared by uniformly mixing the above-described cosmetic raw materialof the present invention with other cosmetic raw materials. Variousmixers and kneaders commonly used in the preparation of cosmeticproducts can be utilized as mixing means. Such equipment is exemplified,for instance, by Homo-Mixers, paddle mixers, Henschel mixers,Homo-Dispersers, colloid mixers, propeller agitators, Homogenizers,inline type continuous emulsifiers, ultrasonic emulsifiers, and vacuumkneaders.

APPLICATION EXAMPLES

Hereinbelow, the present invention is explained in detail by referringto application examples. In the examples, the word “viscosity” refers tovalues obtained at 25° C. In addition, the evaluation of thecharacteristics of the cosmetic raw materials was carried out inaccordance with the methods described below.

[Characteristics Of Cosmetic Raw Materials]

Water Repellency

After coating the cosmetic raw material on a glass plate, a vinylpolymer film on its surface was obtained by drying at room temperatureto remove the solvent. A drop of water was placed on the surface of thecoating film and the contact angle of the water drop was measured. Anautomatic contact angle meter (from Kyowa Interface Science Co., Ltd.)was used for measurement.

Skin-Oil Resistance

50 ml squalane was placed in a 100-ml beaker, whereupon a vinyl polymerfilm obtained in the same manner as described above was immersed thereinovernight and subsequently subjected to visual assessment of changes inits external appearance. Cases, in which no changes were noted weredesignated as ◯, and cases, in which the coating film was swollen weredesignated as x.

Glass Transition Temperature

The glass transition temperature was measured using a differentialscanning calorimeter (DSC).

Tactile Sensation Produced by Coating Films

After coating the cosmetic raw material on a glass plate, a vinylpolymer film on its surface was obtained by drying at room temperatureto remove the solvent. The tactile sensation produced by the surface ofthe coating film was evaluated by finger touch.

Application Example 1

43 g methyl methacrylate, 17 g n-butyl acrylate, 10 g fluorinatedorganic group-containing vinyl monomer (1) represented by the formula:

30 g carbosiloxane dendrimer represented by the formula:

1.5 g 2,2′-azobis-2-methylbutyronitrile (from Otsuka Chemical Co.,Ltd.), and 100 g toluene were placed in a 300-ml 4-necked flask fittedwith an agitator, a temperature gauge, and a reflux tube and stirred for6 hours under heating at 70 to 80° C. in a nitrogen atmosphere. Afterstirring, the product of the reaction was analyzed using gaschromatography, which showed that a vinyl polymer had been obtained at apolymer conversion ratio of 97%. The toluene solution of the vinylpolymer was subjected to 30-min. heat treatment at 140° C. at a reducedpressure of 10 mm Hg to remove the toluene and unreacted monomer. Adispersion of the vinyl polymer containing 20 wt % of nonvolatile matter(hereinafter referred to as “cosmetic raw material (A)”) was prepared byadding 80 g cyclic dimethyl silicone (5-mer) to 20 g of the thusobtained vinyl polymer having carbosiloxane dendritic structures andfluorinated organic groups. Its characteristics are listed in Table 1.

Application Example 2

23 g methyl methacrylate, 17 g n-butyl acrylate, 30 g fluorinatedorganic group-containing vinyl monomer (1) used in Application Example1, 30 g carbosiloxane dendrimer used in Application Example 1, 1.5 g2,2′-azobis-2-methylbutyronitrile (from Otsuka Chemical Co., Ltd.), and100 g toluene were placed in a 300-ml 4-necked flask fitted with anagitator, a temperature gauge, and a reflux tube and stirred for 6 hoursunder heating at 70 to 80° C. in a nitrogen atmosphere. After stirring,the product of the reaction was analyzed using gas chromatography, whichshowed that a vinyl polymer had been obtained at a polymer conversionratio of 96%. The toluene solution of the vinyl polymer was subjected to30-min. heat treatment at 140° C. at a reduced pressure of 10 mm Hg toremove the toluene and unreacted monomer. A dispersion of the vinylpolymer containing 20 wt % of nonvolatile matter (hereinafter referredto as “cosmetic raw material (B)”) was prepared by adding 80 g cyclicdimethyl silicone (5-mer) to 20 g of the thus obtained vinyl polymerhaving carbosiloxane dendritic structures and fluorinated organicgroups. Its characteristics are listed in Table 1.

Application Example 3

43 g methyl methacrylate, 17 g n-butyl acrylate, 10 g fluorinatedorganic group-containing vinyl monomer (2) represented by the formula:

30 g carbosiloxane dendrimer used in Application Example 1, 1.5 g2,2′-azobis-2-methylbutyronitrile (from Otsuka Chemical Co., Ltd.), and100 g toluene were placed in a 300-ml 4-necked flask fitted with anagitator, a temperature gauge, and a reflux tube and stirred for 6 hoursunder heating at 70 to 80° C. in a nitrogen atmosphere. After stirring,the product of the reaction was analyzed using gas chromatography, whichshowed that a vinyl polymer had been obtained at a polymer conversionratio of 96%. The toluene solution of the vinyl polymer was subjected to30-min. heat treatment at 140° C. at a reduced pressure of 10 mm Hg toremove the toluene and unreacted monomer. A dispersion of the vinylpolymer containing 20 wt % of nonvolatile matter (hereinafter referredto as “cosmetic raw material (C)”) was prepared by adding 80 g cyclicdimethyl silicone (5-mer) to 20 g of the thus obtained vinyl polymerhaving carbosiloxane dendritic structures and fluorinated organicgroups. Its characteristics are listed in Table 1.

Application Example 4

43 g methyl methacrylate, 17 g n-butyl acrylate, 15 g methacrylic acid,10 g fluorinated organic group-containing vinyl monomer (1) used inApplication Example 1, 15 g carbosiloxane dendrimer used in ApplicationExample 1, 1.5 g 2,2′-azobis-2-methylbutyronitrile (from Otsuka ChemicalCo., Ltd.), and 100 g isopropyl alcohol were placed in a 300-ml 4-neckedflask fitted with an agitator, a temperature gauge, and a reflux tubeand stirred for 6 hours under heating at 70 to 80° C. in a nitrogenatmosphere. After stirring, the product of the reaction was analyzedusing gas chromatography, which showed that a vinyl polymer had beenobtained at a polymer conversion ratio of 95%. The isopropyl alcoholsolution of the vinyl polymer was subjected to 30-min. heat treatment at140° C. at a reduced pressure of 10 mm Hg to remove the isopropylalcohol and unreacted monomer. After adding 20 g ethanol to 20 g of thethus obtained vinyl polymer having carbosiloxane dendritic structuresand fluorinated organic groups and making a dispersion, 3.68 gtriethanolamine was added thereto. Subsequently, a dispersion of thevinyl polymer containing 20 wt % of nonvolatile matter (hereinafterreferred to as “cosmetic raw material (D)”) was prepared by furtheradding 74.72 g ethanol. Its characteristics are listed in Table 1.

Comparative Example 1

53 g methyl methacrylate, 17 g n-butyl acrylate, 30 g carbosiloxanedendrimer used in Application Example 1, 1.5 g2,2′-azobis-2-methylbutyronitrile (from Otsuka Chemical Co., Ltd.), and100 g toluene were placed in a 300-ml 4-necked flask fitted with anagitator, a temperature gauge, and a reflux tube and stirred for 6 hoursunder heating at 70 to 80° C. in a nitrogen atmosphere. After stirring,the product of the reaction was analyzed using gas chromatography, whichshowed that a vinyl polymer had been obtained at a polymer conversionratio of 97%. The toluene solution of the vinyl polymer was subjected to30-min. heat treatment at 140° C. at a reduced pressure of 10 mm Hg toremove the toluene and unreacted monomer. A dispersion of the vinylpolymer containing 20 wt % of nonvolatile matter (hereinafter referredto as “cosmetic raw material (E)”) was prepared by adding 80 g cyclicdimethyl silicone (5-mer) to 20 g of the thus obtained vinyl polymerhaving carbosiloxane dendritic structures. Its characteristics arelisted in Table 1.

Comparative Example 2

53 g methyl methacrylate, 17 g n-butyl acrylate, 15 g methacrylic acid,15 g carbosiloxane dendrimer used in Application Example 1, 1.5 g2,2′-azobis-2-methylbutyronitrile (from Otsuka Chemical Co., Ltd.), and100 g isopropyl alcohol were placed in a 300-ml 4-necked flask fittedwith an agitator, a temperature gauge, and a reflux tube and stirred for6 hours under heating at 70 to 80° C. in a nitrogen atmosphere. Afterstirring, the product of the reaction was analyzed using gaschromatography, which showed that a vinyl polymer had been obtained at apolymer conversion ratio of 95%. The isopropyl alcohol solution of thevinyl polymer was subjected to 30-min. heat treatment at 140° C. at areduced pressure of 10 mm Hg to remove the isopropyl alcohol andunreacted monomer. After adding 20 g ethanol to 20 g of the thusobtained vinyl polymer having carbosiloxane dendritic structures andmaking a dispersion, 3.68 g triethanolamine was added thereto.Subsequently, a dispersion of the vinyl polymer containing 20 wt % ofnonvolatile matter (hereinafter referred to as “cosmetic raw material(F)”) was prepared by further adding 74.72 g ethanol. Itscharacteristics are listed in Table 1.

TABLE 1 Application Examples Comparative Examples 1 2 3 4 1 2 Cosmeticraw material A B C D E F Methyl methacrylate  43 parts  23 parts  43parts  43 parts  53 parts  53 parts n-Butyl acrylate  17 parts  17 parts 17 parts  17 parts  17 parts  17 parts Methacrylic acid — — —  15 parts—  15 parts Carbosiloxane dendrimer  30 parts  30 parts  30 parts  15parts  30 parts  15 parts Fluorinated organic group-containing  10 parts 30 parts —  10 parts — — vinyl monomer (1) Fluorinated organicgroup-containing — —  10 parts — — — vinyl monomer (2)2,2′-azobis-2-methylbutyronitrile  1.5 parts  1.5 parts  1.5 parts  1.5parts  1.5 parts  1.5 parts Polymerization solvent Toluene, Toluene,Toluene, IPA, 100 Toluene, IPA, 100 100 parts 100 parts 100 parts parts100 parts parts Water repellency (contact angle) 109 109 112 109 107 107Skin-oil resistance ◯ ◯ ◯ ◯ X X Glass transition temperature (° C.)  47 32  21 No meas.  46 No meas. Tactile sensation produced by ExcellentExcellent Slight Excellent Excellent Excellent coating film stickinessnoted

Application Example 5

<Lipstick>

55 parts by weight of cosmetic raw material (A), 20 parts by weight of adimethylpolysiloxane with a viscosity of 2 mPa·s having both ends of themolecular chain blocked by trimethylsiloxy groups, 5 parts by weight ofliquid lanolin, 3.8 parts by weight of castor oil, and 8 parts by weightof glyceryl triisostearate were mixed under heating at 85° C. Afterthat, an oil base liquid lipstick was prepared by further adding 0.1parts by weight of an anti-oxidant, 0.1 parts by weight of fragrance,2.0 parts by weight of silicone-treated titanium oxide, 2 parts byweight of Red No. 201, 1 part by weight of Red No. 202, and 3 parts byweight of Yellow No. 4 aluminum lake, uniformly mixing the ingredients,deaerating the mixture, and filling a container with it. The thusobtained lipstick was evaluated in accordance with the methods describedbelow. The results are shown in Table 2.

In addition, no changes in the external appearance of the lipstick werenoted after allowing it to stand for 3 months at room temperature, whichconfirmed the excellent compounding stability of the cosmetic rawmaterial of the present invention.

Feel on Application

A group of 10 panelists applied the lipstick to the lips and evaluatedits spreadability, stickiness, and moisturizing feel produced. Theresults of the evaluation were represented in the following manner:cases, in which 8 to 10 people reported that the lipstick was easilyspreadable, non-sticky, and produced a moisturized skinfeel, weredesignated as ◯, those, in which 4 to 7 people reported the same, weredesignated as Δ, and those, in which 3 or fewer people reported thesame, were designated as x.

Color Transfer

After applying the lipstick to the lips, a group of 10 panelists presseda piece of tissue paper to the lips for 5 seconds and evaluated thepresence/absence of color transfer. The results of the evaluation wererepresented in the following manner: cases, in which 8 to 10 peoplereported that no traces of the lipstick were noticed on the tissuepaper, were designated as ◯, those, in which 4 to 7 people reported thesame, were designated as Δ, and those, in which 3 or fewer peoplereported the same, were designated as x.

Long-term Adhesion

A group of 10 panelists applied the lipstick to the lips and performedwork indoors for 8 hours at a temperature of 28 to 32° C. and a humidityof 60% or higher, whereupon the presence/absence of remainders oflipstick on the lips was confirmed by finger touch. The results of theevaluation were represented in the following manner: cases, in which 8to 10 people reported remainders of adhered lipstick, were designated as◯, those, in which 4 to 7 people reported the same, were designated asΔ, and those, in which 3 or fewer people reported the same, weredesignated as x.

Application Example 6

<Lipstick>

With the exception of using cosmetic raw material (B) instead ofcosmetic raw material (A) in Application Example 5, an oil base liquidlipstick was prepared in the same manner as in Application Example 5.The resultant lipstick was evaluated in the same manner as inApplication Example 5, and the results were also listed in Table 2.

In addition, no changes in the external appearance of the lipstick werenoted after allowing it to stand for 3 months at room temperature, whichconfirmed the excellent compounding stability of the cosmetic rawmaterial of the present invention.

Comparative Example 3

<Lipstick>

With the exception of using cosmetic raw material (E) instead ofcosmetic raw material (A) in Application Example 5, an oil base liquidlipstick was prepared in the same manner as in Application Example 5.The resultant lipstick was evaluated in the same manner as inApplication Example 5, and the results were also listed in Table 2.

TABLE 2 Application Application Comparative Example 5 Example 6 Example3 Spreadability ◯ ◯ ◯ Stickiness ◯ ◯ ◯ Moisturized sensation ◯ ◯ ◯ Colortransfer ◯ ◯ ◯ Long-term adhesion ◯ ◯ X

Application Example 7

<Mascara>

62 parts by weight of cosmetic raw material (B), 15 parts by weight of adextrin fatty acid ester and 4.5 parts by weight of low-boilingisoparaffin were added to 51 parts of isoparaffin under heating toprepare a dispersion, which was then mixed with 2 parts by weight ofhydrophobic treated silicic anhydride, 1.5 parts by weight of organicbentonite, 7 parts by weight of black iron oxide powder, and 10 parts byweight of mica. Mascara was prepared by filling a container with themixture. The thus obtained mascara was evaluated in accordance with themethods described below. The results were listed in Table 3.

In addition, no changes in the external appearance of the mascara werenoted after allowing it to stand for 3 months at room temperature, whichconfirmed the excellent compounding stability of the cosmetic rawmaterial of the present invention.

Feel on Application

A group of 10 panelists applied the mascara to the eyelashes andevaluated its spreadability. The results of the evaluation wererepresented in the following manner: cases, in which 8 to 10 peoplereported that the mascara was easily spreadable, were designated as ◯,those, in which 4 to 7 people reported the same, were designated as Δ,and those, in which 3 or fewer people reported the same, were designatedas x.

Curling Properties

A group of 10 panelists applied the mascara to the eyelashes andevaluated its curling properties. The results of the evaluation wererepresented in the following manner: cases, in which 8 to 10 peoplereported that the mascara exhibited curling properties, were designatedas ◯, those, in which 4 to 7 people reported the same, were designatedas Δ, and those, in which 3 or fewer people reported the same, weredesignated as x.

Long-term Adhesion

A group of 10 panelists applied the mascara to the eyelashes andperformed work indoors for 8 hours at a temperature of 28 to 32° C. anda humidity of 60% or higher, whereupon the presence/absence ofremainders of mascara was confirmed by finger touch. The results of theevaluation were represented in the following manner: cases, in which 8to 10 people reported presence of remainders of mascara, were designatedas ◯, those, in which 4 to 7 people reported the same, were designatedas Δ, and those, in which 3 or fewer people reported the same, weredesignated as x.

Comparative Example 4

<Mascara>

With the exception of using cosmetic raw material (E) instead ofcosmetic raw material (B) in Application Example 7, mascara was preparedin the same manner as in Application Example 7. The resultant mascarawas evaluated in the same manner as in Application Example 7, and theresults were also listed in Table 3.

TABLE 3 Application Example 7 Comparative Example 4 Spreadability ◯ ◯Curling properties ◯ ◯ Long-term adhesion ◯ X

Application Example 8

<Nail Polish>

A nail polish was prepared by uniformly mixing 40 parts by weight ofcosmetic raw material (A), 15 parts by weight of nitrocellulose, 10parts by weight of acetyl tributyl citrate, 2 parts by weight ofcamphor, 5 parts by weight of ethyl acetate, 10 parts by weight of butylacetate, 16 parts by weight of toluene, 1 part by weight of organicbentonite, and 1 part by weight of pigment, and then filling a containerwith the mixture. The thus obtained nail polish was evaluated inaccordance with the methods described below. The results were listed inTable 4.

In addition, no changes in the external appearance of the nail polishwere noted after allowing it to stand for 3 months at room temperature,which confirmed the excellent compounding stability of the cosmetic rawmaterial of the present invention.

Feel on Application

A group of 10 panelists applied the nail polish to the fingernails andevaluated its spreadability and the smoothness of the film formed afterdrying. The results of the evaluation were represented in the followingmanner: cases, in which 8 to 10 people reported that the nail polish waseasily spreadable and provided excellent smoothness, were designated as◯, those, in which 4 to 7 people reported the same, were designated asΔ, and those, in which 3 or fewer people reported the same, weredesignated as x.

Long-term Adhesion

A group of 10 panelists applied the nail polish to the fingernails andperformed work indoors for 8 hours at a temperature of 28 to 32° C. anda humidity of 60% or higher, whereupon the amount of remaining adherednail polish was evaluated by visual inspection. The results of theevaluation were represented in the following manner: cases, in which 8to 10 people reported that the condition of the residual nail polish wasthe same as immediately upon application, were designated as ◯, those,in which 4 to 7 people reported the same, were designated as Δ, andthose, in which 3 or fewer people reported the same, were designated asx.

Water Repellency

The nail polish was applied to the fingernails of 10 panelists anddried, whereupon drops of water were placed on the fingernails and waterrepellency was evaluated based on the extent to which the water dropscould stick to or were repelled by the surface. The results of theevaluation were represented in the following manner: cases, in which 8to 10 people reported that the water drops were repelled by the nailpolish, were designated as ◯, those, in which 4 to 7 people reported thesame, were designated as Δ, and those, in which 3 or fewer peoplereported the same, were designated as x.

Application Example 9

<Nail Polish>

With the exception of using cosmetic raw material (C) instead ofcosmetic raw material (A) in Application Example 8, a nail polish wasprepared in the same manner as in Application Example 8. The resultantnail polish was evaluated in the same manner as in Application Example8, and the results were also listed in Table 4.

Comparative Example 5

<Nail Polish>

With the exception of using cosmetic raw material (E) instead ofcosmetic raw material (A) in Application Example 8, a nail polish wasprepared in the same manner as in Application Example 8. The resultantnail polish was evaluated in the same manner as in Application Example8, and the results were also listed in Table 4.

TABLE 4 Application Application Comparative Example 8 Example 9 Example5 Spreadability ◯ ◯ ◯ Coating film smoothness ◯ ◯ ◯ Long-term adhesion ◯◯ X Water repellency ◯ ◯ Δ

Application Example 10

<Skin Cream-Type Cosmetic Product>

A skin cream cosmetic material was prepared by putting 15 parts byweight of cosmetic raw material (A), 2 parts by weight ofsilicone-treated titanium oxide powder, 10 parts by weight of octylp-methoxycinnamate, 12 parts by weight of a dimethylpolysiloxane with aviscosity of 20 mPa·s having both ends of the molecular chain blocked bytrimethylsiloxy groups, 3 parts by weight of polyoxyethylene (40-moladduct) hydrogenated castor oil, 60 parts by weight of squalane, 5 partsby weight of glycerin, 3 parts by weight of beeswax, a small amount ofantiseptic, a small amount of fragrance, and an suitable amount ofpurified water in a Henschel mixer and stirring the ingredients for 10minutes at 1500 rpm. The thus obtained cosmetic material was evaluatedin accordance with the methods described below. The results were listedin Table 5.

In addition, no changes in the external appearance of the skincream-type cosmetic material were noted after allowing it to stand for 3months at room temperature, which confirmed the excellent compoundingstability of the cosmetic raw material of the present invention.

Feel on Application

A group of 10 panelists applied the cream to the back of the hands andevaluated its spreadability and skin feel. The results of the evaluationwere represented in the following manner: cases, in which 8 to 10 peoplereported that the cosmetic material was easily spreadable, did notproduce an unpleasant sensation and produced an excellent skin feel,were designated as ◯, those, in which 4 to 7 people reported the same,were designated as Δ, and those, in which 3 or fewer people reported thesame, were designated as x.

Long-term Adhesion

A group of 10 panelists applied the cream to the wrists, spreading andrubbing it in thoroughly with fingers, and performed work indoors for 8hours at a temperature of 28 to 32° C. and a humidity of 60% or higher.Subsequently, the presence/absence of remainders of adhered cream wasevaluated after bending the wrists 50 times. The results of theevaluation were represented in the following manner: cases, in which 8to 10 people reported that there was some cream left, were designated as◯, those, in which 4 to 7 people reported the same, were designated asΔ, and those, in which 3 or fewer people reported the same, weredesignated as x.

Water Repellency

After applying and thoroughly spreading the cream on the backs of thehands of 10 panelists, the panelists washed hands with liquid soap andwiped them with a towel. After that, water drops were applied to thebacks of the hands and water repellency was evaluated based on theextent to which the water drops could stick to or were repelled by thesurface. The results of the evaluation were represented in the followingmanner: cases, in which 8 to 10 people reported that the water dropswere repelled, were designated as ◯, those, in which 4 to 7 peoplereported the same, were designated as Δ, and those, in which 3 or fewerpeople reported the same, were designated as x.

Comparative Example 6

<Skin Cream-Type Cosmetic Product>

With the exception of using cosmetic raw material (E) instead of 15parts by weight of cosmetic raw material (A) in Application Example 10,a skin cream-type cosmetic material was prepared in the same manner asin Application Example 10. The cream-type cosmetic material wasevaluated in the same manner as in Application Example 10, and theresults were also listed in Table 5.

TABLE 5 Application Example 10 Comparative Example 6 Spreadability ◯ ΔSkin feel ◯ ◯ Long-term adhesion ◯ X Water repellency ◯ Δ

Application Example 11

<Shampoo>

A shampoo was prepared by mixing 20 parts by weight of the disodium saltof sulfosuccinic acid monoester, 2 parts by weight of lauroyldiethanolamide, 5 parts by weight of cosmetic raw material (C), 0.2parts by weight of fragrance, 0.1 parts by weight of antiseptic, 72.5parts by weight of purified water, and a trace amount of colorant andfilling a container with the mixture. The thus obtained shampoo wasevaluated in accordance with the methods described below. The resultsare shown in Table 6.

Post-Washing Assessment

The gloss and luster of hair was visually evaluated by 10 panelistsafter washing the hair with the shampoo and drying it. The results ofthe evaluation were represented in the following manner: cases, in which8 to 10 people reported that the hair was glossy and lustrous, weredesignated as ◯, those, in which 4 to 7 people reported the same, weredesignated as Δ, and those, in which 3 or fewer people reported thesame, were designated as x.

Long-term Adhesion

The presence/absence of residual shampoo was evaluated by 10 panelistsby finger touch after washing the hair with the shampoo and drying it.The results of the evaluation were represented in the following manner:cases, in which 8 to 10 people reported presence of residual adheredshampoo, were designated as ◯, those, in which 4 to 7 people reportedthe same, were designated as Δ, and those, in which 3 or fewer peoplereported the same, were designated as x.

Water Repellency

After washing the hair with the shampoo and drying it, 10 panelistsevaluated water repellency by spraying water drops on the hair andassessing how well the water drops were repelled by the hair. Theresults of the evaluation were represented in the following manner:cases, in which 8 to 10 people reported good water repellency, weredesignated as ◯, those, in which 4 to 7 people reported the same, weredesignated as Δ, and those, in which 3 or fewer people reported thesame, were designated as x.

Comparative Example 7

<Shampoo>

With the exception of using 5 parts by weight of cosmetic raw material(E) instead of cosmetic raw material (C) in Application Example 11, ashampoo was prepared in the same manner as in Application Example 11.The shampoo was evaluated in the same manner as in Application Example11, and the results were also listed in Table 6.

TABLE 6 Application Example 11 Comparative Example 7 Gloss and luster ◯◯ after washing hair Long-term adhesion ◯ X Water repellency ◯ Δ

Application Example 12

<Hair Spray>

An aerosol hair spray was prepared by mixing 100 parts by weight ofcosmetic raw material (D), 50 parts by weight of ethanol, and 35 partsby weight of liquefied petroleum gas under cooling conditions. The thusobtained hair spray was evaluated in accordance with the methodsdescribed below. The results are shown in Table 7.

Hair Gloss and Luster

10 panelists had their hair sprayed with the hair spray and styled.After setting, the gloss and luster of the hair were visually evaluated.The results of the evaluation were represented in the following manner:cases, in which 8 to 10 people reported that the hair was glossy andlustrous, were designated as ◯, those, in which 4 to 7 people reportedthe same, were designated as Δ, and those, in which 3 or fewer peoplereported the same, were designated as x.

Hair Set Retention Properties

After curling the hair, it was treated with the hair spray. Afterwearing a wet towel for 5 minutes, 10 panelists evaluated curlretention. The results of the evaluation were represented in thefollowing manner: cases, in which 8 to 10 people reported curlretention, were designated as ◯, those, in which 4 to 7 people reportedthe same, were designated as Δ, and those, in which 3 or fewer peoplereported the same, were designated as x.

Long-term Adhesion

10 panelists had their hair sprayed with the hair spray and styled, and,after setting, performed work indoors for 8 hours at a temperature of 28to 32° C. and a humidity of 60% or higher. Subsequently, thepresence/absence of residual hair spray was confirmed by finger touch.The results of the evaluation were represented in the following manner:cases, in which 8 to 10 people reported presence of adhered hair spray,were designated as o, those, in which 4 to 7 people reported the same,were designated as A, and those, in which 3 or fewer people reported thesame, were designated as x.

[Comparative Example 8]

<Hair Spray>

With the exception of using cosmetic raw material (F) instead ofcosmetic raw material (D) in Application Example 12, a hair spray wasprepared in the same manner as in Application Example 12. The hair spraywas evaluated in the same manner as in Application Example 12, and theresults were also listed in Table 7.

TABLE 7 Application Comparative Example 12 Example 8 Hair gloss andluster ◯ ◯ Hair set retention properties ◯ X Long-term adhesion ◯ X

1. A cosmetic raw material comprising a vinyl polymer, wherein the vinylpolymer is a copolymer selected from the group consisting of A, B and C;and A and C wherein: (A) vinyl monomers containing fluorinated organicgroups in the molecule, (B) vinyl monomers that do not have fluorinatedorganic groups in the molecule, and (C) carbosiloxane dendrimers, havingradical polymerizable organic groups, represented by the general formula(III):

wherein Y is a radical polymerizable organic group, R¹ is an aryl oralkyl group with 1 to 10 carbon atoms, and X^(i) is a silylalkyl grouprepresented by the following formula (II)

wherein R¹ is the same described as above, R² is an alkylene group with2 to 10 carbon atoms, R³ is an alkyl group with 1 to 10 carbon atoms,and X^(i+1) is a group selected from the group comprising hydrogenatoms, aryl groups and alkyl groups with 1 to 10 carbon atoms, andsilylalkyl groups X^(i), wherein superscript

 is an integer of 1 to 10 indicating the generation of the silylalkylgroup, starting in each carbosiloxane dendritic structure with a valueof 1 for the X^(i) group in the formula (III), and the subscript

 is an integer of 0 to 3, said vinyl polymer having a copolymerizationratio of component (A) to component (B) of 0.1 to 100:99.9 to 0 wt %,and a co-polymerization ratio of the total of component (A) andcomponent (B) to component (C) of 0.1 to 99.9 :99.9 to 0.1 wt %.
 2. Thecosmetic raw material according to claim 1, wherein the radicalpolymerizable organic group Y in component (C) is a group selected fromthe group consisting of organic groups containing acrylic and organicgroups containing methacrylic groups represented by the general formula:

wherein R⁴ is a hydrogen atom or methyl, and R⁵ is an alkylene groupwith 1 to 10 carbon atoms and

wherein R⁴ and R⁵ are as defined above, organic groups containingalkenylaryl groups represented by the general formula:

wherein R⁶ is a hydrogen atom or methyl, R⁷ is an alkyl group with 1 to10 carbon atoms, R⁸ is an alkylene group with 1 to 10 carbon atoms,

 is an integer of 0 to 4, and

 is 0 or 1, and, alkenyl groups with 2 to 10 carbon atoms.
 3. Thecosmetic raw material according to claim 1, which is a solution ordispersion comprising the vinyl polymer containing carbosiloxanedendritic structures and fluorinated organic groups, and a liquidselected from the group consisting of silicone oil, organic oil,alcohol, and water.
 4. A cosmetic product obtained by compounding thecosmetic raw material according to claim
 1. 5. A cosmetic productaccording to claim 4, which is intended for topical application to skin.6. A method for manufacturing a cosmetic product, said method comprisingthe step of mixing a cosmetic raw material according to claim 1 withother raw materials.